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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Revision of the Thermodynamics of the Proton in Gas Phase
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Revision of the Thermodynamics of the Proton in Gas Phase

机译：气相中质子热力学的修订

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Proton transfer is ubiquitous in various physical/chemical processes, and the accurate determination of the thermodynamic parameters of the proton in the gas phase is useful for understanding and describing such reactions. However, the thermodynamic parameters of such a proton are usually determined by assuming the proton as a classical particle whatever the temperature. The reason for such an assumption is that the entropy of the quantum proton is not always soluble analytically at all temperatures. Thereby, we addressed this matter using a robust and reliable self-consistent iterative procedure based on the Fermi-Dirac formalism. As a result, the free proton gas can be assumed to be classical for temperatures higher than 200 K. However, it is worth mentioning that quantum effects on the gas phase proton motion are really significant at low temperatures (T <= 120 K). Although the proton behaves as a classical particle at high temperatures, we strongly recommend the use of quantum results at all temperatures, for the integrated heat capacity and the Gibbs free energy change. Therefore, on the basis of the thermochemical convention that ignores the proton spin, we recommend the following revised values for the integrated heat capacity and the Gibbs free energy change of the proton in gas phase and, at the standard pressure (1 bar): triangle H0 -> T = 6.1398 kJ mol(-1) and triangle G0 -> T = -26.3424 kJ mol(-1). Finally, it is important noting that the little change of the pressure from 1 bar to 1 atm affects notably the entropy and the Gibbs free energy change of the proton.
机译：质子转移在各种物理/化学过程中无处不在，并且准确确定气相中质子的热力学参数对于理解和描述这种反应是有用的。然而，这种质子的热力学参数通常通过假设质子为经典粒子而与温度无关来确定。这种假设的原因是，量子质子的熵并不总是在所有温度下都能解析地溶解。因此，我们使用了基于Fermi-Dirac形式主义的鲁棒且可靠的自洽迭代过程来解决此问题。结果，可以假设游离质子气体在200 K以上的温度下是经典的。但是，值得一提的是，在低温下（T <= 120 K），对气相质子运动的量子效应确实非常重要。尽管质子在高温下表现为经典粒子，但我们强烈建议在所有温度下使用量子结果，以实现综合热容量和吉布斯自由能变化。因此，根据忽略质子自旋的热化学惯例，我们建议以下修正值用于气相和标准压力（1 bar）下质子在气相中的综合热容量和吉布斯自由能变化：三角形H0-> T = 6.1398 kJ mol（-1）和三角形G0-> T = -26.3424 kJ mol（-1）。最后，重要的是要注意，压力从1 bar到1 atm的微小变化会显着影响质子的熵和吉布斯自由能变化。

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